Artificial Photosynthesis for Solar Fuels - an Evolving Research Field within AMPEA, a Joint Programme of the European Energy Research Alliance

On the path to an energy transition away from fossil fuels to sustainable sources, the European Union is for the moment keeping pace with the objectives of the Strategic Energy Technology-Plan. For this trend to continue after 2020, scientific breakthroughs must be achieved. One main objective is to produce solar fuels from solar energy and water in direct processes to accomplish the efficient storage of solar energy in a chemical form. This is a grand scientific challenge. One important approach to achieve this goal is Artificial Photosynthesis. The European Energy Research Alliance has launched the Joint Programme "Advanced Materials & Processes for Energy Applications” (AMPEA) to foster the role of basic science in Future Emerging Technologies. European researchers in artificial photosynthesis recently met at an AMPEA organized workshop to define common research strategies and milestones for the future. Through this work artificial photosynthesis became the first energy research sub-field to be organised into what is designated "an Application” within AMPEA. The ambition is to drive and accelerate solar fuels research into a powerful European field - in a shorter time and with a broader scope than possible for individual or national initiatives. Within AMPEA the Application Artificial Photosynthesis is inclusive and intended to bring together all European scientists in relevant fields. The goal is to set up a thorough and systematic programme of directed research, which by 2020 will have advanced to a point where commercially viable artificial photosynthetic devices will be under development in partnership with industr

Representing Fitness Landscapes by Valued Constraints to Understand the Complexity of Local Search

Local search is widely used to solve combinatorial optimisation problems and to model biological evolution, but the performance of local search algorithms on different kinds of fitness landscapes is poorly understood. Here we introduce a natural approach to modelling fitness landscapes using valued constraints. This allows us to investigate minimal representations (normal forms) and to consider the effects of the structure of the constraint graph on the tractability of local search. First, we show that for fitness landscapes representable by binary Boolean valued constraints there is a minimal necessary constraint graph that can be easily computed. Second, we consider landscapes as equivalent if they allow the same (improving) local search moves; we show that a minimal normal form still exists, but is NP-hard to compute. Next we consider the complexity of local search on fitness landscapes modelled by valued constraints with restricted forms of constraint graph. In the binary Boolean case, we prove that a tree-structured constraint graph gives a tight quadratic bound on the number of improving moves made by any local search; hence, any landscape that can be represented by such a model will be tractable for local search. We build two families of examples to show that both the conditions in our tractability result are essential. With domain size three, even just a path of binary constraints can model a landscape with an exponentially long sequence of improving moves. With a treewidth two constraint graph, even with a maximum degree of three, binary Boolean constraints can model a landscape with an exponentially long sequence of improving moves

Basic science232. Certolizumab pegol prevents pro-inflammatory alterations in endothelial cell function

Background: Cardiovascular disease is a major comorbidity of rheumatoid arthritis (RA) and a leading cause of death. Chronic systemic inflammation involving tumour necrosis factor alpha (TNF) could contribute to endothelial activation and atherogenesis. A number of anti-TNF therapies are in current use for the treatment of RA, including certolizumab pegol (CZP), (Cimzia ®; UCB, Belgium). Anti-TNF therapy has been associated with reduced clinical cardiovascular disease risk and ameliorated vascular function in RA patients. However, the specific effects of TNF inhibitors on endothelial cell function are largely unknown. Our aim was to investigate the mechanisms underpinning CZP effects on TNF-activated human endothelial cells. Methods: Human aortic endothelial cells (HAoECs) were cultured in vitro and exposed to a) TNF alone, b) TNF plus CZP, or c) neither agent. Microarray analysis was used to examine the transcriptional profile of cells treated for 6 hrs and quantitative polymerase chain reaction (qPCR) analysed gene expression at 1, 3, 6 and 24 hrs. NF-κB localization and IκB degradation were investigated using immunocytochemistry, high content analysis and western blotting. Flow cytometry was conducted to detect microparticle release from HAoECs. Results: Transcriptional profiling revealed that while TNF alone had strong effects on endothelial gene expression, TNF and CZP in combination produced a global gene expression pattern similar to untreated control. The two most highly up-regulated genes in response to TNF treatment were adhesion molecules E-selectin and VCAM-1 (q 0.2 compared to control; p > 0.05 compared to TNF alone). The NF-κB pathway was confirmed as a downstream target of TNF-induced HAoEC activation, via nuclear translocation of NF-κB and degradation of IκB, effects which were abolished by treatment with CZP. In addition, flow cytometry detected an increased production of endothelial microparticles in TNF-activated HAoECs, which was prevented by treatment with CZP. Conclusions: We have found at a cellular level that a clinically available TNF inhibitor, CZP reduces the expression of adhesion molecule expression, and prevents TNF-induced activation of the NF-κB pathway. Furthermore, CZP prevents the production of microparticles by activated endothelial cells. This could be central to the prevention of inflammatory environments underlying these conditions and measurement of microparticles has potential as a novel prognostic marker for future cardiovascular events in this patient group. Disclosure statement: Y.A. received a research grant from UCB. I.B. received a research grant from UCB. S.H. received a research grant from UCB. All other authors have declared no conflicts of interes

A density functional study of oxygen atom transfer reactions between biological oxygen atom donors and molybdenum(IV) bis(dithiolene) complexes

Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me3NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)(2)](2-) and [Mo(OCH3)(mnt)(2)](-) (mnt = maleonitrile-1,2-dithiolate), which may serve as models for mononuclear molybdenum enzymes of the DMSO reductase family. The reaction between [MoO(mnt)(2)](2-) and trimethylamine N-oxide was found to have an activation energy of 72 kJ/mol and proceed via a transition state (TS) with distorted octahedral geometry, where the MOO is bound through the oxygen to the molybdenum atom and the N-O bond is considerably weakened. The computational modeling of the reactions between dimethyl sulfoxide (DMSO) and [MoO(mnt)(2)](2-) or [Mo(OCH3)(mnt)(2)](-) indicated that the former is energetically unfavorable while the latter was found to be favorable. The addition of a methyl group to [MoO(mnt)(2)](2-) to form the corresponding des-oxo complex not only lowers the relative energy of the products but also lowers the activation energy. In addition, the reaction with [Mo(OCH3)(mnt)(2)](-) proceeds via a TS with trigonal prismatic geometry instead of the distorted octahedral TS geometry modeled for the reaction between [MoO(mnt)(2)](2-) and Me3NO

Atomic structure of cobalt oxide nanoparticles active in light driven catalysis of water oxidation

The atomic structure of water-oxidizing nanoparticles (10–60 nm) formed from cobalt(II) salts and methylenediphosphonate (M2P) is investigated. These amorphous nanoparticles are of high interest for production of solar fuels. They facilitate water oxidation in a directly light-driven process using [Ru(bpy)3]2+ (bpy = 2,2’-bipyridine) as a photosensitizer and persulfate (S2O82−) as an electron acceptor. By X-ray absorption spectroscopy (XAS) at the cobalt K-edge, cobalt L-edge and oxygen K-edge, we investigate the light- driven transition from the CoII/M2P precursor to the active catalyst, which is a layered cobalt(III) oxide with structural similarities to water-oxidizing electrocatalysts. The M2P ligand likely binds at the periphery of the nanoparticles, preventing their further agglomeration during the catalytic reaction. This system opens a possibility to link the catalytically active nanoparticles via a covalent bridge to a photosensitizer and build an artificial photosynthetic system for direct utilization of solar energy for fuel production without production of electricity as an intermediate step. This article is part of a Special Issue entitled: Photosynthetic and Biomimetic Hydrogen Production

Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands: reactivity studies of a functional model for molybdenum oxotransferases

Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N, N-bis(2-pyridylmethyl) amine (L - OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6- results in the formation of [MoO2(L - O)] PF6. Similarly, the reaction of N-(2-mercaptobenzyl)- N,N-bis(2-pyridylmethyl) amine (L -SH) with MoO2(acac)(2) leads to the formation of [MoO2(L - S)](+). The dioxo-molybdenum complex [MoO2(L - O)](+) reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV) O(L - O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L - O)] PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [( L - O) OMo(mu-O) MoO(L - O)](PF6)(2). The crystal structures of [MoO2(L - O)] PF6 and the mu-oxo bridged dimer are presented